Aluminum Phosphinate and Phosphates of Salen Ligands

A new dealkylation reaction between organophosphate esters and Salen aluminum bromide compounds has been
used to prepare three new aluminum salen compounds salen(tBu)AlOP(O)Ph2 (1) (salen = N,N‘-ethylenebis(3,5-di-tert-butylsalicylideneimine)), [(MeOH)Alsalen(tBu){OMePO2(O)}Alsalen(tBu){OMePO2(O)}Alsalen(tBu)]Br (2), and
[salpen(tBu)AlO]2[(BuO)2PO]2 (3) (salpen = N,N‘-propylenebis(3,5-di-tert-butylsalicylideneimine)). Compounds 1·MeOH, 2, and 3 were characterized by single-crystal X-ray diffraction. Compound 1 is the first example of a
monomeric aluminum Schiff base phosphinate. Compound 2 is a cationic Salen aluminum phosphate, and compound
3 contains an aluminophosphate ring. This work is the first example of the intentional use of an aluminum-based
dealkylation reaction to form new compounds.

本研究利用磷酸酯与Salen溴化铝配合物（Salen aluminum bromide）之间的新型脱烷基反应，合成了三种新型Salen铝配合物：salen(tBu)AlOP(O)Ph₂（1，其中salen = N,N'-亚乙基双(3,5-二叔丁基水杨醛亚胺)）、[(MeOH)Alsalen(tBu){OMePO₂(O)}Alsalen(tBu){OMePO₂(O)}Alsalen(tBu)]Br（2）以及[salpen(tBu)AlO]₂[(BuO)₂PO]₂（3，其中salpen = N,N'-亚丙基双(3,5-二叔丁基水杨醛亚胺)）。通过单晶X射线衍射（single-crystal X-ray diffraction）对配合物1·MeOH、2和3进行了结构表征。配合物1是首例单核铝基希夫碱（Schiff base）次膦酸酯配合物；配合物2为阳离子型Salen铝磷酸盐配合物，配合物3则含有铝磷酸盐环结构。本工作首次采用基于铝的脱烷基反应定向合成新型化合物。